Asphalt coating material and process of producing same



April 16, 1935. w. A". CRAIG ET AL ASPHALT COATING MATERIAL AND PROCESS OF PRODUCING SAME Filed April 11, 1.953'

mi ui YPatented Apr. 16, 1935 t Y* s Ywas PATE;

Nrw-CFM@ fAsPHALi coATING MATERIAL ANn o rnocnss or PRODUCING SAME l allace `ACraig,' Los Angeles, and Fred E. Grif- I y thLong Beach, Calif.,` assignors to William C; McDuie, receiver for Richfield Oil Company of CaliforniaLosrAngeles, Calif., a corporation -of Delaware AppiiatonfAprru `11, 1933, seriarNo. 665,524 A9 claims. (c1. 10e- 61) This invention relates to a new asphaltic cement or coating `material and the processl of producing.

thesame.

Processes `for the manufacture. of asphaltV by` 5 oxidationnof` petroleum oilor petroleum oil residua used to decolorize "gasoline,

ing oil stocks,` and` l1 Withfair "are known 1in `the art, and alsothe mixing of V'asphalt- With comnnnuted solids, such as sand, clay, diatomaceous earth, rock dust and `the like,- to modify` `the [characteristics of the asphalt.n It isggenerallybelieved that the` incorporation of comminuted solids increases the useful life `of the asphalt When such a mixture is yapplied to roofing paper, composition shingles, varidroth'evr surfaces that are exposed to the elements, particularlybright sunshine. "Such a mixture also finds application in the manufacture of a VVariety of other products Where `adense asphaltic cement is needed for binding, cementing or, waterproofing purposes.

Heretofore, fdifticultyjhas been experienced producing `an asphaltic materialv entirely suitable for the; ,manufacturefoff rooing` felt,` asphalt shingles,=battery boxesffand the like, invvhich relatively high flash `anldLhigh melting point products are required,` and which twill have suitable ductility under stress.` 4`We havedeterminedthat this is due to producing products which are ,not

i uniformlymxidized, inWhich-some part of,lthe

. asphaltic oil"has been overfxidized While "other parts have. notbeenjsuiiieiently oxidized to give the required nielting point`,"ash point and duc'- tiuty. y i j g Weh'ave now jdiscovered that these ,difculties maybe overcome by o'iiidizingthe oil in the presence of -aj'suitable 'agentgwith `which a, required non-destructive oxidizing action; may be eiected Y more uniforzgomyr mei-equine degree, and at the Sametime incorporate finely divided solidjmaterial Which imparts to thief finished 'product fthe severe Weather conditions.

The catalyzers or Contact agents ourprocessfareg (1) VClarifying Vand Adecolorizng agents that are kerosene or `lubricatability to v vithstan'd4 disintegration caused by employed in ,2 .1i"ir1f 1yv gruldpetroieum Geket The decolorizingagentsare `materials such as fullers earth, the hydrousfmagnsium silicatesiof the"talc`and serpentine `divvisionas specified in A Syste'mfof.,- Mineralogy. by lEdu/fard Salisbury i Dana. sixtheditton, page 669, and clays consisting of hydro'ussilicatesv ofpaluminum,v such as `montmorillonit`e, bentonite andjthe like,` and which may. or maynot have been processed to "summarized as follows v j o l. A closer bond is obtained between thefsolid r fparticlesandthe asphalt. d

improve their decolorizing' efficiency,Vv and activated charcoals of 'animal orV vegetable or1g1n which have decolorizing properties.'

The clarifying and decolorizing agents, when g brought` into contact With petroleum products, become coated with an adsorbed layer of asphalticl material orpolymerized hydrocarbons, which We have determined are benecial toasphaltic coat-g either during `the processing of lubricating oil or other `petroleum products prior, to incorporating the"decolor izing agent with .the material tobe oxidized, or it may beformed during the process herein described., Also, due to the source'and'the t method of `producing petroleum coke', asimilar condition exists upon the surfaces of thecoke grains." 'y l "The manufacturer ofjfthis'material may takeplacefin any 'suitable' receptacle in whichfinti-` mate contact of airA and liquid may be eiected. The characteristics of `th e.iinished product may be Varied by varying the temperature, timeof processing, proportion of air and steamused for blowing, or charging ingredients,'either singly or in combination.y For instancesimilar results may bejobtained when either an unused decolorjizing agent or a'spent agent is used'in the process. rIt is our belief that when an unused agent isemployed, it goesthrough a preliminary'stage similar to'thatlvvhich 'occurs when it isused. in processing` lubricating oil. In other Words,' we have determined that adsorption and polymerizat ing material. This adsorbed layer may bevformerd r o tion occur upon the Asurfaces of thek grains of the' solid'materials. This reaction aids in the formation of `the nished product, as the reduction to the grade desired isaccomplished in less time in the presence of these agents.`

those obtained from the materials describedjheretofore. t t r The benets to be derived by producing an asphaltic material as described' herein may be v2. Polymerization on thesurfaces of the solid particles' accelerates the-reduction of the charge tothe desired consistency. Y

3. Conversion-or` utilization of materials Athat are `frequently discarded by the industry into -5 commercially useful material is effected. This is particularly true when spent decolorizing agents are used. In addition to the agent, there is the lubricating oil that is commingled with it, amounting to approximately 25 per cent. In our process this lubricatingoil is converted into asphalt.- With respect to the use of petroleum coke, any oil that may be admixed with the coke will be converted into asphaltic material.

4. A variety of grades of' asphaltic cement or coating material, superior to materials now available, may be produced.

An object of the invention is to produce a new asphaltic cement or coating material which will have a relatively high melting point, and at the same time have a suitable ductility. It is also our object to produce a product that will have a relatively long useful life whenexposed to varying Weather conditions.

Another object of the invention is to produce an asphaltic cement or. coating material by a simple and efficient process, in which the various characteristics of the finished product may be controlled in order to meet the requirements of the various industries which may have occasion to use such a product.

Another'y object of the invention is to utilize spentclarifying and decolorizing agents, and at theV same time recover in a useful form that oil which is intimately mixed with these decolorizing agents. f

Another object is to prepare a new and useful product from petroleum coke. y Various other objects and advantages of the Ypresent invention will be apparent from the description of the preferred example of the new product and process embodying the invention. For this purpose reference is made to .the accompanying drawing, in which there is illustrated a form of apparatus in which the invention may be performed.

In the drawing, similar numbers represent similar parts. v t

lFigure I is a center longitudinal ,sectional view of a still or chamber, equipped with air and steam induction pipes, an oilcharging pipe, vapor outlet pipes,'a conveyor and chute for introducing contact agent, and furnace means to supply heat to the chamber. n

Figure II is a detail transverse sectional view taken on line A-A of Figure IL In Figure I, 3 represents generally a still. or chamber for holding a bulk supply mixture of the oil and contact agent. Still 3 is illustrated as being of cylindrical form, horizontally arranged in furnace setting 4. Still 3 is equipped with a manhole and removable coverv plate 5. Stationed above manhole and cover plate 5 is chute (i and a belt conveyor 1 for introducing spent clarifying` and decolorizing agent into still 3. A charging pipe 8, controlled by valve 9, connects still 3 at the top to a source of the petroleum oil residuum to be processed.

A draw o pipe I0, controlled by valves Il and I2, connects stillY 3 at the bottom to Ya storage, or barrel filling device, not shown. Pipes I3 and I4 connect still 3 at the top to a vapor line'or pipe I5. Vapor line or pipe I5 is connected to a condenser not shown.` `Furnace setting 4 is provided with fire box I6, burner I'I and flue I8 which leads to a smokestack-not shown.

Anair and steam inlet pipe 2I extendsjlongitudinallyy over still 3 at one side of the same, and Y is connected to a series of banch pipes I9 which enterstill 3 at short intervals throughout 'S length and reach nearly to the bottom. These branch pipes I9 are bent nearl the open end so as to conform to the curvature of the still or chamber. The flow'of air, steam, or air and steam through these branch pipes I3 is controlled byvalves 2Il. Steam pipe 22, controlled by valve 2li, and air pipe 23, controlled by valve 25, con-V nect steam and air inlet pipe 2| to a source of :steam and air respectively.

The preferred process for the production of the new asphaltic' coating material, as carried out in the apparatus described, is as follows:

A bulk supply of an asphalt base or a mixed base petroleumY oil residuum, having a gravity which may range from approximately 10 to 17 A. P. I., is charged into still 3 through charging pipe 8 with valve 9 open.` Valve 9 is then closed andk thevbulk supplyy of oil is agitated and commingled with the required amount of spent clarifying and decolorizing agent, or other contact material, which may range from approximately 5 per .cent by weight to as high as 50 per cent of the agent, the exact quantity and type used de- 'A pending upon the product desired.

Theagent is introduced into still 3rthrough man hole 5 by'means of conveyor 1 and chute 6, and the mixing or commingling of the oil and agent is effected by introduction of air under sufficient pressure through pipes 23, 2| and I9, controlledv and regulated by operation of valves 25 and 2I'I. Pipes I9 forma bend near the open end, as illustrated in Figure II, so as to conform approximately to the curvature of the still, in order that the introduction of the air may produce a circulatory agitation and prevent deposition of the agent on the bottom of the still.

After the agent and `oil to be processed have been v,co'mmingled and substantially uniformly mixed, the mixture is heated and maintained at a temperature ranging from approximately 400 to 550F. by the application of heat from burner I1, the products of combustion passing around the bottom of still 3, through re box IS, and out through flue or smoke tunnel I8 to a smoke stack not shown; or the heating of the oil and agent may be commenced before or during the mixing operation. I

The introduction of air is continued fora period of time ranging fromy 10 to 30 hours, at a rate sucient to maintain the oil and agentuniformly mixed, and also to effect an oxidation thereof to the required degree. The quantityr of air employed may range from approximately 500 cubic feetper minutefto 1200 cubic feet per minutefor a 200 barrel batch of mixed oil'and agent, the exact quantity/of air kused and temperatures` employed depending upon the grade of oil processed,.the per cent of agent employed and the product desired. l

In the manufacture of certain grades of this new asphaltic product, steam may be used in conjunction with the air, in which case, after the mixed oiland agent has attained a temperature above 212 F., valve `211, in steam pipe 22 is opened to a degree sufficient to allow the necessary amount of steam to pass into pipe 2 I, wherein it mixes with the incoming air from pipe 23 and passes along with the air through valves 2U, pipes I 9, and then into still 3. Steam is employed when it is desired-tov modify the rate of oxidation and separate a larger per cent of low boiling distillatefrom the residual oil.A

.ized oil and steam, if used, pass out of still 3 throughpipes I3 and |74, and then into vvapori line l5, which conducts the same to a condenser not shown, wherein the vaporized oil products and water vapor are condensed and separated from the aeriform products.Y Y

When theasphaltic oil Vcontaining the spent agent has been oxidized to the required degree to produce the desired grade of asphaltic cementy or coating material, the introduction of air, steam, or `steam and air is discontinued and the charge is drawn oi through pipe I0, by. opening valves H and I2, into a storage, or through a barrel filling device and barreled for shipment to the trade, to be used thereafter for coating roofing felt, making battery boxes, orcoating other surfaces, as heretofore stated.

While the process herein described isA well vfor the manufacture of roofing felt, asphalt Y shingles, battery boxes and the like, comprising,

uniformlyy oxidized asphalt base petroleum oil residuum Vcontaining comminuted clarifying `and decolorizing agent dispersed through the mass, and bonded to said oxidized residuum by a film of polymerized hydrocarbonsderived from a petroleum oil distillate, said asphalt composition .being produced by oxidizing asphalt base petroleum oil residuum, y commingled with a spent clarifying and decolorizing agent derived from petroleum.

oil reiining processes, `with air. at temperatures ranging from 400 to 550` F. f

` 2. A high melting, ductile asphalt composi-v tion, comprising, uniformly oxidized asphalt base petroleum oil residuum containing comminuted clarifying and decolorizing agent dispersed through the mass, and bondedto said oxidized residuum by a lm of polymerized hydrocarbons derived from a petroleumoil distillate, said asphalt composition beingproduced by agitating asphalt base petroleum oil residuum, commingled with spent clarifying andv decolorizing agent derived from` petroleum oil refining processes, with air at temperatures ranging from 400 to 550 F.

s `for a period of time ranging from 10 to 30 hours.

3. A process of producing a high melting, ducmingling the agentwith the oil stock, separating `the coated agent frornftheoil stock, mixing the coated agent vWith asphalt base petroleum oil residuum, then oxidizing and reducing the mix- ,ture by blowing with air to anasphalt consistency, 'at an oxidizing temperature ranging from approximately 400 vto"5`50"l'.`,` for a period of time l not less than tenhours.l

4. A process of producing a high melting, ductile asphalt composition Vfor the manufacture of roong felt, asphalt shingles, battery boxes and the like, comprising, coating a clarifying and decolorizingr agent with polymerized l hydrocarbons by commingling the agent with a petroleum lubricating oil stock, and then oxidizing the commingled mixture by blowing With air to an asphalt consistency, at an oxidizing temperature ranging from 400 to 550 F., for a period of time ranging from Vten to thirty hours.

' 5. A'process of producing a high melting, ductile asphalt composition for the manufacture of roong felt, asphalt shingles, battery boxes and the like, comprising, treating petroleum lubricating oil distillate with a clarifying and decolorizing agent, separating the agent and a minor portion of the ,distillate from a majorportion of the distillate, mixing the separated agent containing `the minor portion of the distillate With'asphalt base petroleum oil residuum, then oxidizing and reducing the mixture by blowing With air to an asphalt consistency, at an oxidizing temperature `ranging from approximately 400 to 550" F. for a i period of time not less than ten hours.

6. A process of producing oxidized asphalt from petroleum oil residuum containing asphalt base petroleum oils, comprising, oxidizing the oil residuum, mixed with a clarifying and decolorizing agent, by blowing the mixture with `air at temperatures ranging from 400 to 550 F. for a period of time ranging from ten to thirty hours, and reducing the mixture to an asphalt consistency.

7. A process of producing oxidized asphalt from petroleum oil rediuum containing asphalt `base petroleum oils, comprising, oxidizing the oil residuum, mixed with a spent clarifying and decolorizing agent, by blowing the mixture with air Vat temperatures ranging from 400 to 550 F. for

a period of time not less than ten hours, and reducing the mixtureto an asphalt consistency.V

l 3. A process'. of producing oxidized asphalt from petroleum oil residuum containing asphalt base oils as the principal constituent, comprising, oxidizing the oil residuum, mixed with a'com' minuted hydrous magnesium silicate of the talc and serpentine division, by blowing the mixture with air for a period of timev of not less than ten hours, at temperatures ranging from 400 to 550 F., and reducing the mixture to an asphalt consistency. v

9. In the process of producing oxidized asphalt from petroleum oil residuum containing asphalt base petroleum oils as the principal ingredient,

the improvement which comprises, Voxidizing the residuum, mixed With spent hydrous magnesium silicate of the talc and serpentine division which has been used in petroleum oil refining processes,

bytblowing the 'mixture'with air for a period of time of not less than ten hours, attemperatures ranging from 400 to 550 F., and reducing the mixtureto an asphalt consistency.

WALLACE A. CRAIG. FRED E. GRIFFITH. 

